OBJECTIVE: To achieve the total synthesis of the aglycone of the antileukemic drug daunomycinone and of the alkaloid dendrobine. APPROACH: The regiospecific synthesis of daunomycinone is to be carried out using a photochemical o-Fries rearrangement of an o-cyanoester derivative of a bicyclic tetralin derivative. Subsequent ring closure would give 9-deoxydaunomycinone. Introduction of C-9 hydroxyl by direct or indirect routes would yield synthetic daunomycinone. Coupling of either aglycone with daunosamine by the Stanford Research Inst. procedure would give total synthetic 9-deoxydaunomycin and daunomycin, respectively.